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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Iron (IV) Formation and the pH Dependent Kinetics of the Fenton Reaction

Despite its widespread importance for biological and environmental chemistry and decades of study, the mechanism underlying the Fenton reaction is still a matter of some controversy. Here, to elucidate the pH dependence of this complex reaction, a new kinetic model is developed to explain the increase in rate and mechanistic shift that occurs from acidic to neutral conditions. This mechanism originated from a re-analysis of a previously proposed model, which neglected explicit iron speciation, leading to unrealistic rate constants. Accounting for speciation suggests a much faster formation rate of Fe(IV), which is estimated to be on the order of 10 6 M −1 s −1 . Expanding on prior kinetic studies that include speciation under acidic conditions, we propose a unified kinetic model that captures the pH-dependent rate acceleration in Fe(II) oxidation by H 2 O 2 , which is a significant step toward resolving the long-standing mechanistic ambiguity of Fenton chemistry.

Cohen, Liron [Lawrence Berkeley National Laborator↗
NASA NTRS1986

Direct solar-pumped iodine laser amplifier

During this period the parametric studies of the iodine laser oscillator pumped by a Vortek simulator were carried out before amplifier studies. The amplifier studies are postponed to the extended period after completing the parametric studies. In addition, the kinetic modeling of a solar-pumped iodine laser amplifier, and the experimental work for a solar pumped dye laser amplifier are in progress. This report contains three parts: (1) a 10 W CW iodine laser pumped by a Vortek solar simulator; (2) kinetic modeling to predict the time to lasing threshold, lasing time, and energy output of solar-pumped iodine laser; and (3) the study of the dye laser amplifier pumped by a Tamarack solar simulator.

Han, K. S.↗
DOE OSTI2025

Nonequilibrium effects in high-gain inertial confinement fusion

Recent experimental demonstrations of ignition and target gain in inertial confinement fusion (ICF) have stimulated interest in exploring the fundamental physics of violent deuterium-tritium (DT) burn in high-gain ICF targets. A significant DT-burn fraction is a necessary condition for high energy gain and large neutron yields (>100MJ). Using classical molecular-dynamics (MD) simulations and a hybrid fluid-kinetic model, we examine how a large fraction of low-energy 𝛼 particles can kick D and T ions out of equilibrium in high-gain ICF targets. The MD results suggest that (1) temperatures of 𝑇 𝐷 and 𝑇 𝑇 can differ by as much as ∼20% of their mean temperature and (2) the deviation of the DT energy distribution from the Maxwell-Boltzmann function can exceed ∼30%. Some of these MD observations, such as the preferential heating of D ions by low-energy 𝛼 particles and the temperature separation, can be explained by a proposed hybrid fluid-kinetic model. Furthermore, the implication of such nonequilibrium effects on the DT reactivity is also discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Interaction of Iron with Alumina Refractory Under Flash Ironmaking Conditions

A novel flash ironmaking technology (FIT) based on the direct reduction of iron ore concentrate by a reducing gas such as hydrogen, natural gas, or coal gas has been developed at the University of Utah. A proper choice of refractories is expected to play an important role in the development of FIT and its scale-up. In this work, the interaction of iron with alumina refractory under flash ironmaking conditions has been investigated. A thermodynamic basis for the interaction phenomena has been developed by considering the Fe-Al-O system, and a kinetic model based on solid-state diffusion is proposed to describe the growth of the hercynite (FeAl{sub 2}O{sub 4}) spinel formed as a result of the interaction between Fe, O (from H{sub 2}O and CO{sub 2}), and Al{sub 2}O{sub 3}. Experiments were conducted with Fe powders and pure Al{sub 2}O{sub 3} in the temperature range 1200 to 1500 °C under gas atmospheres relevant to flash ironmaking, and the reacted samples were analyzed using XRD, SEM-EDX, and EPMA techniques. The analyses of reacted samples confirmed the formation of the hercynite (FeAl{sub 2}O{sub 4}) spinel phase and the thickness of the FeAl{sub 2}O{sub 4} spinel as measured using elemental line scans in SEM-EDX and EPMA varied in the range of 0.5 to 1.3 mm. Results showed that the proposed model suitably describes the growth of the hercynite spinel layer, which obeyed the parabolic rate law at all temperatures. The parabolic rate constants were obtained and the diffusion-controlled growth of the FeAl{sub 2}O{sub 4} layer strongly depended on temperature. Furthermore, using the kinetic model, an expression for the effective diffusivity ( (D{sub eff})-bar ) was obtained and its values at the experimental temperatures were determined. The solid-state diffusion was an activated process, as expected, with an activation energy value of 231 kJ/mol.

36 MATERIALS SCIENCE↗
DOE OSTI2019

The impacts of ionization chemistry on hydrocarbon detonation [Thesis]

As carbon emissions are negatively impacting ecosystems across the globe, researchers are in a race against time to provide cleaner and more efficient power. Detonation engines can help meet the increasing demands for cleaner and more efficient power generation by providing an alternative means to use oxy-fuel combustion for carbon sequestration. By pairing a detonation engine with a magnetohydrodynamic (MHD) generator, power can be directly extracted from the ionized gases behind the detonation front via the Lorentz force. This eliminates the moving components found in gas turbine engines, which are unable to withstand high temperatures encountered in oxy-fuel combustion. The electrical conductivity of the ionized gas behind the detonation front can be increased by several orders of magnitude with the addition of readily ionizing seed particles such as potassium, increasing the power generation of the engine. However, this increase has a limit as dilution studies have shown decreases in detonation speeds with increasing diluent. To better understand the interaction of seed particles with the detonation front and the electrical conductivity of the mixed gas, a detailed hydrocarbon kinetic model has been created in conjunction with a detonation solver. This model is, to my knowledge, the first detailed hydrocarbon model to be used in detonation simulations. I used this model to study the parasitic interaction arising from using potassium seed material. I found that the ionization of the seed particles negatively impacted detonation velocities up to 8% and power production up to 15%, pointing to the need for further research development into detonation kinetic models and ionization fields.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
NASA NTRS1992

A parametric analysis of radiative structure in aerobrake shock layers

A broad-spectrum version of the NEQAIR code was modified to account for self-absorption and applied to AFE flowfields calculated by the LAURA code with a variety of kinetic models. The resulting radiative fluxes were obtained in a decoupled fashion from the flowfield solver along the vehicle's stagnation streamline. The radiative flux obtained was broken down by causative process to study the radiative structure of the AFE's flowfield for the various kinetic models. In addition, the radiative fluxes for several points on a typical AFE trajectory were analyzed to examine how the radiative structure changes as the vehicle completes its aeropass. Only two radiative processes dominated the stagnation radiative flux, and the flow field conditions near the wal were found to exert considerable influence over the radiative flux to the wall.

Greendyke, Robert B.↗
NASA NTRS2012

Experimental and Modeling Investigation of the Effect of Air Preheat on the Formation of NOx in an RQL Combustor

The Rich-burn/Quick-mix/Lean-burn (RQL) combustor concept has been proposed to minimize the formation of oxides of nitrogen (NOx) in gas turbine systems. The success of this low-NOx combustor strategy is dependent upon the links between the formation of NOx, inlet air preheat temperature, and the mixing of the jet air and fuel-rich streams. Chemical equilibrium and kinetics modeling calculations and experiments were performed to further understand NOx emissions in an RQL combustor. The results indicate that as the temperature at the inlet to the mixing zone increases (due to preheating and/or operating conditions) the fuel-rich zone equivalence ratio must be increased to achieve minimum NOx formation in the primary zone of the combustor. The chemical kinetics model illustrates that there is sufficient residence time to produce NOx at concentrations that agree well with the NOx measurements. Air preheat was found to have very little effect on mixing, but preheating the air did increase NOx emissions significantly. By understanding the mechanisms governing NOx formation and the temperature dependence of key reactions in the RQL combustor, a strategy can be devised to further reduce NOx emissions using the RQL concept.

Gas Turbine Engines↗
DOE OSTI2020

Ignition delay time and speciation of dibutyl ether at high pressures

Dibutyl ether (DBE) is a promising biofuel due to its high cetane number (~ 100) and high volumetric energy density (31.6 MJ/L). It could either be used directly in compression ignition engines or blended with other conventional or renewable fuels. Oxidation and pyrolysis kinetics of DBE are not well known, particularly at high pressures. In this work, we have experimentally investigated the chemical kinetics of DBE in three domains: (a) ignition delay time measurements in a rapid compression machine over T = 550–650 K, P = 10, 20, 40 bar, φ = 0.5, 1; (b) ignition delay time measurements in a shock tube over T = 900–1300 K, P = 20, 40 bar, φ = 0.5, 1; (c) laser-based carbon monoxide speciation measurements in a shock tube during DBE pyrolysis and oxidation over T = 1100–1400 K, P = 20 bar. Pressure time-histories measured in RCM experiments exhibited unique 3-stage and 4-stage ignition behavior predominantly at fuel-lean conditions. Experimental data were compared with the predictions of two recent chemical kinetic models of DBE. Sensitivity analyses were carried out to identify key reactions which may have caused the discrepancy between experiments and simulations. We found that the rate of decomposition of DBE may need to be revisited to improve the oxidative and pyrolytic predictions of DBE kinetic model.

09 BIOMASS FUELS↗
NASA NTRS2000

Accelerated Aging of Lead-Free Propellant

Following higher than expected 2-NDPA depletion rates in a lead-free doublebase formulation (RPD-422), an accelerated aging study was conducted to verify the depletion rates. A test plan was prepared to compare the aging characteristics of lead-free propellant and NOSIH-AA2. The study was also designed to determine which lead-free ballistic modifiers accelerated 2-NDPA depletion. The increased depletion rate occurred in propellants containing monobasic copper salicylate. Four lead-free propellants were then formulated to improved aging characteristics over previous lead-free propellant formulations. The new formulations reduced or replaced the monobasic copper salicylate. The new formulations had improved aging characteristics. Their burn rates, however, were unacceptable for use in a 2.75 inch rocket. To compare aging characteristics, stabilizer depletion rates of RPD-422, AA2, M28, and RLC 470/6A were measured or taken from the literature. The data were fit to a kinetic model. The model contained first and zero order terms which allowed the stabilizer concentration to go to zero. In the model, only the concentration of the primary stabilizer was considered. Derivatives beyond the first nitrated or nitroso derivative of 2-NPDA were not considered. The rate constants were fit to the Arrhenius equation and extrapolated to lower temperatures. The time to complete stabilizer depletion was estimated using the kinetic model. The four propellants were compared and the RPD-422 depleted faster at 45 C than both A22 and M28. These types of predictions depend on the validity of the model and on confidence in the Arrhenius relationship holding at lower temperatures. At 45 C, the zero order portion of the model dominates the depletion rate.

Furrow, Keith W.↗
NASA NTRS1985

Direct solar-pumped iodine laser amplifier

This semiannual progress report covers the period from April 1, 1985 to Sept. 30, 1985 under NASA grant NAS1-441 entitled direct solar pumped iodine laser amplifier. During this period the parametric studies of the iodine laser oscillator pumped by a Vortek simulator was carried out before the amplifier studies. The amplifier studies are postponed to the extended period following completion of the parametric studies. In addition, the kinetic modeling of a solar pumped iodine laser amplifier, and the experimental work for a solar pumped dye laser amplifier are in progress. This report contains three parts: (1) the radiation characteristics of solar simulator and the parametric characteristics of photodissociation iodine laser continuously pumped by a Vortek solar simulator; (2) kinetic modeling of a solar pumped iodine laser amplifier; and (3) the study of the dye laser amplifier pumped by a Tamarack solar simulator.

Han, K. S.↗
NASA NTRS2009

Nitric Oxide and Oxygen Air-Contamination Effects on Extinction Limits of Non-Premixed Hydrocarbon-Air Flames for a HIFiRE Scramjet

Unique nitric oxide (NO) and oxygen air-contamination effects on the extinction Flame Strength (FS) of non-premixed hydrocarbon (HC) vs. air flames are characterized for 7 gaseous HCs, using a new idealized 9.3 mm straight-tube Opposed Jet Burner (OJB) at 1 atm. FS represents a laminar strain-induced extinction limit based on cross-section-average air jet velocity, Uair, that sustains combustion of a counter jet of gaseous fuel just before extinction. Besides ethane, propane, butane, and propylene, the HCs include ethylene, methane, and a 64 mole-% ethylene / 36 % methane mixture, the writer s previously recommended gaseous surrogate fuel for HIFiRE scramjet tests. The HC vs. clean air part of the work is an extension of a May 2008 JANNAF paper that characterized surrogates for the HIFiRE project that should mimic the flameholding of reformed (thermally- or catalytically-cracked) endothermic JP-like fuels. The new FS data for 7 HCs vs. clean air are thus consolidated with the previously validated data, normalized to absolute (local) axial-input strain rates, and co-plotted on a dual kinetically dominated reactivity scale. Excellent agreement with the prior data is obtained for all 7 fuels. Detailed comparisons are also made with recently published (Univ. Va) numerical results for ethylene extinction. A 2009-revised ethylene kinetic model (Univ. Southern Cal) led to predicted limits within approx. 5 % (compared to 45 %, earlier) of this writer s 2008 (and present) ethylene FSs, and also with recent independent data (Univ. Va) obtained on a new OJB system. These +/- 5 % agreements, and a hoped-for "near-identically-performing" reduced kinetics model, would greatly enhance the capability for accurate numerical simulations of surrogate HC flameholding in scramjets. The measured air-contamination effects on normalized FS extinction limits are projected to assess ongoing Arc-Heater-induced "facility test effects" of NO production (e.g., 3 mole-%) and resultant oxygen depletion (from 21 to 19.5 %), for testing the "64/36" surrogate fuel in Langley s Arc-Heated Scramjet Test Facility for HIFiRE engine designs. The FS results show a generally small (< 4 %) "nitric oxide enhancement" effect, relative to clean air, for up to 3 % NO (freestream Mach number up to 7 in Arc Jet testing). However, a progressively large "oxygendeficiency weakening" effect develops. For 3 % NO, a net weakening of 26 % in FS is derived for the "64/36" fuel vs. air. The corresponding net weakening for pure ethylene is 20 %. A number of practical recommendations regarding facility test effects are offered.

Pellett, Gerald L.↗
NASA NTRS2011

Experimental and Modeling Studies of the Combustion Characteristics of Conventional and Alternative Jet Fuels. Final Report

The objectives of this project have been to develop a comprehensive set of fundamental data regarding the combustion behavior of jet fuels and appropriately associated model fuels. Based on the fundamental study results, an auxiliary objective was to identify differentiating characteristics of molecular fuel components that can be used to explain different fuel behavior and that may ultimately be used in the planning and design of optimal fuel-production processes. The fuels studied in this project were Fischer-Tropsch (F-T) fuels and biomass-derived jet fuels that meet certain specifications of currently used jet propulsion applications. Prior to this project, there were no systematic experimental flame data available for such fuels. One of the key goals has been to generate such data, and to use this data in developing and verifying effective kinetic models. The models have then been reduced through automated means to enable multidimensional simulation of the combustion characteristics of such fuels in real combustors. Such reliable kinetic models, validated against fundamental data derived from laminar flames using idealized flow models, are key to the development and design of optimal combustors and fuels. The models provide direct information about the relative contribution of different molecular constituents to the fuel performance and can be used to assess both combustion and emissions characteristics.

Meeks, Ellen↗
DOE OSTI2022

Oxyanion Surface Complexes Control the Kinetics and Pathway of Ferrihydrite Transformation to Goethite and Hematite

The rate and pathway of ferrihydrite (Fh) transformation at oxic conditions to more stable products is controlled largely by temperature, pH, and the presence of other ions in the system such as nitrate (NO 3 - ), sulfate (SO 4 2- ), and arsenate (AsO 4 3- ). Although the mechanism of Fh transformation and oxyanion complexation have been separately studied, the effect of surface complex type and strength on the rate and pathway remains only partly understood. We have developed a kinetic model that describes the effects of surface complex type and strength on Fh transformation to goethite (Gt) and hematite (Hm). Two sets of oxyanion-adsorbed Fh samples were prepared, nonbuffered and buffered, aged at 70 ± 1.5 °C, and then characterized using synchrotron X-ray scattering methods and wet chemical analysis. Kinetic modeling showed a significant decrease in the rate of Fh transformation for oxyanion surface complexes dominated by strong inner-sphere (SO 4 2- and AsO 4 3- ) versus weak outer-sphere (NO 3 - ) bonding and the control. The results also showed that the Fh transformation pathway is influenced by the type of surface complex such that with increasing strength of bonding, a smaller fraction of Gt forms compared with Hm. In conclusion, these findings are important for understanding and predicting the role of Fh in controlling the transport and fate of metal and metalloid oxyanions in natural and applied systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Modeling electron beam irradiation of methane

We built a chemical kinetic model for the electron beam irradiation of methane and report simulation results with dose rates ranging from 2 to 200 kGy s -1 at 298 K and 1 atm pressure. The model contains 92 species and 778 gas-phase reactions. We report the time evolution of concentrations of stable products (including H 2 , C 2 H 6 , C 3 H 8 , C 2 H 4 , C 3 H 6 , C 4 H 10 , C 2 H 2 , and C 3 H 4 ) as well as some radicals and ions. Here we discuss how yields of products depend on dose rate and how they change during the course of irradiation. To understand the processes controlling product formation, we quantify the extent to which various reactions produce and destroy major products and the key radicals and ions. Normalized sensitivity coefficients are computed for the production of stable products to gain further insight into factors controlling product yields. We were able to reduce the mechanism to 63 species and 331 reactions while incurring less than 5% error in the final concentrations of stable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Thermophysics Characterization of Kerosene Combustion

A one-formula surrogate fuel formulation and its quasi-global combustion kinetics model are developed to support the design of injectors and thrust chambers of kerosene-fueled rocket engines. This surrogate fuel model depicts a fuel blend that properly represents the general physical and chemical properties of kerosene. The accompanying gaseous-phase thermodynamics of the surrogate fuel is anchored with the heat of formation of kerosene and verified by comparing a series of one-dimensional rocket thrust chamber calculations. The quasi-global combustion kinetics model consists of several global steps for parent fuel decomposition, soot formation, and soot oxidation, and a detailed wet-CO mechanism. The final thermophysics formulations are incorporated with a computational fluid dynamics model for prediction of the combustor efficiency of an uni-element, tri-propellant combustor and the radiation of a kerosene-fueled thruster plume. The model predictions agreed reasonably well with those of the tests.

Wang, Ten-See↗
NASA NTRS2001

Thermophysics Characterization of Kerosene Combustion

A one-formula surrogate fuel formulation and its quasi-global combustion kinetics model are developed to support the design of injectors and thrust chambers of kerosene-fueled rocket engines. This surrogate fuel model depicts a fuel blend that properly represents the general physical and chemical properties of kerosene. The accompanying gaseous-phase thermodynamics of the surrogate fuel is anchored with the heat of formation of kerosene and verified by comparing a series of one-dimensional rocket thrust chamber calculations. The quasi-global combustion kinetics model consists of several global steps for parent fuel decomposition, soot formation, and soot oxidation and a detailed wet-CO mechanism to complete the combustion process. The final thermophysics formulations are incorporated with a computational fluid dynamics model for prediction of the combustion efficiency of an unielement, tripropellant combustor and the radiation of a kerosene-fueled thruster plume. The model predictions agreed reasonably well with those of the tests.

Wang, Ten-See↗
DOE OSTI2022

Time-resolved CO 2 , CO, and N 2 vibrational population measurements in Ns pulse discharge plasmas

Abstract Time-resolved CO 2 and N 2 vibrational populations and translational-rotational temperature are measured in a CO 2 –N 2 plasma sustained by a ns pulse discharge burst in plane-to-plane geometry. Time-resolved, absolute number density of CO generated in the plasma is also inferred from the experimental data. CO 2 and CO vibrational populations are measured by mid-IR, tunable quantum cascade laser absorption spectroscopy, and N 2 vibrational populations are measured by the ns broadband vibrational CARS. Transient excitation of N 2 and CO 2 asymmetric stretch vibrational energy modes is detected during the discharge burst. The time-resolved rate of CO generation does not correlate with N 2 or CO 2 ( ν 3 ) vibrational temperatures, indicating that CO 2 dissociation via the vibrational excitation is insignificant at the present conditions. The rate of CO generation decreases gradually during the discharge burst. The estimated specific energy cost of the CO product is close to that of N atoms in pure nitrogen, measured previously at similar operating conditions. Comparison of the experimental data with the kinetic modeling analysis indicates that CO 2 dissociation in collisions with electronically excited N 2 molecules is the dominant channel of CO generation at the present conditions, although the inferred CO yield in these processes is significantly lower than 1. The effect of vibrational energy transfer between N 2 and CO 2 on the plasma chemical processes is insignificant. The kinetic model underpredicts a rapid reduction of the N 2 and CO 2 ( ν 3 ) vibrational temperatures during the later half of the discharge burst and in the afterglow. V–T relaxation of N 2 by N and O atoms generated in the ns pulse discharge plasma does not affect the vibrational relaxation rate in a significant way. However, rapid V–T relaxation of CO 2 by O atoms has a significant effect on the relaxation rate. The difference between the experimental data and the modeling predictions may be due to the unknown scaling of the CO 2 –O V–T rates with the vibrational quantum number.

Physics↗
DOE OSTI2019

Rate of MgO Pickup in Alumina Inclusions in Aluminum-Killed Steel

This work aims to clarify the rate and mechanism of MgO pickup by alumina inclusions and the effect of oxide impurities in MgO crucibles on this transformation. Two MgO crucibles from different batches from the same supplier were used in laboratory experiments with Al-killed steel. A kinetic model was developed, based on mass-transfer control in the liquid steel. Rate constants were fitted using inclusion analysis. The rate of magnesium transfer from the two types of crucibles was found to differ by a factor of 20; faster magnesium transfer was associated with formation of a slag layer on the inner surface of the crucible wall (rather than a solid spinel product layer). The kinetic model was also used to simulate industrial scale ladle refining (1) to illustrate the effects of total oxygen concentration and (2) to evaluate the contribution of steel-refractory reaction (in addition to steel-slag reaction) on the rate of MgO pickup in alumina inclusion. The rate of MgO pickup was higher with a lower inclusion concentration. For ladle desulfurization, the extent of MgO pickup in inclusions is directly linked to the extent of desulfurization; both reactions are controlled by the oxygen potential at the steel-slag interface.

36 MATERIALS SCIENCE↗